Jackson, WRc

23 November 2002

NOTICE OF CORRECTIONS TO THIS PAGE

With reference to the main content of this page, we received a letter, (21 Nov. 2002), from Karen McLintock, Company Secretary of WRc plc. She is also Company Secretary for WRc-NSF Limited. Ms McLintock is concerned about our ‘misuse’ of the Company name “Water Research Centre” which, she explains, belongs to WRc plc. She also suggested that the original title for the item below, (UK Water Research Centre “Report” exposed as bad science), was “potentially libellous.” See Ms McLintock’s letter.

Information on the WRc-NSF website indicates that “WRc-NSF Ltd – [is] a joint venture of WRc plc and NSF International.” Confusingly, the WRc-NSF document under discussion (below) is labelled WRc Ref: CO 5037 JULY 2002. The URL for that document is – http://www.bfsweb.org/documents/wrcreport.pdf and the email address for WRc-NSF is – wrcnsf @ wrcplc.co.uk. The email address or Mr Peter Jackson, who works for WRc-NSF Ltd, is even more perplexing – jackson_p @ wrcplc.co.uk!

Because the NPWA does not deliberately mislead the public, we are more than happy to acknowledge that WRc plc and WRc-NSF Ltd, while sharing the same email addresses ( @ wrcplc ) and Company Secretary, are separate legal entities. We have made the corrections requested by Ms McLintock and apologise to her and to any companies, and/or subsidiaries and/or groups with which the forementioned legal entities may now be, or may at any time have been associated. Apart from those corrections, the comments on Mr Jackson’s report – submitted by Myron Coplan, Doug Cross and NPWA – remain the unedited.

Now, to return to the matter at hand – please read the comments on the WRc-NSF report by Mr Peter Jackson entitled: “Chemistry and bioavailability aspects of fluoride in drinking water, WRc Ref: CO 5037.” At the request of Ms McLintock, the title has been changed.

Theoretical modelling for hire:

Making science fit preconceived notions?

When NPWA discovered that the chemicals (silicofluorides) used in artificial fluoridation schemes in the UK had FAILED FORMAL VOTE in Europe, we contacted the relevant Committee and were referred to personnel at the WRc-NSF Ltd (which we had formerly referred to, inaccurately, as “Water Research Centre”). The main correspondent, Dr Peter Jackson of WRc-NSF was on that Committee. He admitted that the chemicals had never been toxicologically tested. [Extracts from these email exchanges were subsequently published on page 2 of our newsletter – Watershed, Vol.8, N0.1, Spring 2002].

In July 2002, however, Dr Jackson co-authored a report which was commissioned by the British Fluoridation Society (and described by them as “an authoritative report”), which, inter alia, purports to confirm that silicofluorides are the same as naturally occurring fluorides and therefore “safe”. He does this by constructing “models”, rather than by carrying out the physical laboratory testing which is essential to get to the truth of the matter. We consider this latest report from the WRc-NSF as part of the plethora of fluoridation propaganda specifically designed to protect a political mindset. It is not based on sound science and is certainly not in the interests of the public health. See Jackson’s report at – http://www.bfsweb.org/documents/wrcreport.pdf

The following critical comments were sent to Dr Jackson by Myron J. Coplan, a chemical engineer; Doug Cross, a forensic ecologist and Jane Jones, Campaign Director of NPWA.

From Myron J Coplan to Peter Jackson

The following comments pertain to your paper titled “Chemistry and Bioavailability Aspects of Fluoride in Drinking Water” are offered on the premise that you and I have a common interest in good science. This differs from the way Ed Urbansky attacked my work as “junk science” before he knew anything about my background.

An expert working for one of the world’s largest phosphate processors said this:

“The chemical formula of fluosilicic acid is H2SiF6. However, things are not as simple as that due to the fact that rarely is fluosilicic acid present as pure H2SiF6…There are well reported references to the existence of H2SiF6·SiF4 [a coordinated compound comprising a fluosilicic acid molecule and a silicon tetrafluoride molecule]…Hereon in this presentation, FSA [fluosilicic acid] means a mixture of HF, H2SiF6 and H2SiF6·SiF4” – – [Where excess silica is available for reaction, SiF6= can in effect be condensed to dimeric [F4SiF2SiF4]= with two bridging fluoride ions joining the silicon atoms. But this anion, too, is only stable in concentrated solutions containing excess HF – IEP]

You must agree that this is an important observation by a contemporary expert in a very arcane subject. It is not an academic matter. Theoretical analyses of the dissociation path of silicofluoride are less than credible if they are based on a mistaken premise. Smith’s view of “fluosilicic acid” ought to be taken to heart by those with the temerity to expound theory on a subject with a century-old history of controversy.

Indeed, even at this late date the EPA’s Urbansky has performed a remarkable entre-chat in hopes of landing upright on his feet. In June this year EPA published a solicitation for help from prospective research entities interested in providing EPA with research assistance in the area of “MEASUREMENT OF FLUOROSILICATES IN DRINKING WATER”

Hexafluorosilicic acid (H2SiF6) and sodium hexafluorosilicate (Na2SiF6) are the most commonly used fluoridating agents by potable water systems in the U.S. These species dissociate and hydrolyze to produce fluoride anion (F -). The release of fluoride proceeds through a complex, multi-step equilibrium process that is not well-understood. A variety of models have been proposed, and the speciation remains a matter of debate as does the existence of some fluorosilicates. A review of the relevant chemical literature detailing with the complexities, disagreement, and scientific facts has been prepared by the EPA. This review is available to prospective applicants, and they are encouraged to request a copy prior to preparing a proposal.

In addition to the silicon (IV) present from the fluoridating agent, many natural water supplies contain soluble oxo-and hydroxosilicates, which further complicates the speciation. The EPA seeks information on the utility of techniques and methods for monitoring the species formed during the dissociation and hydrolysis of hexafluorosilicate as well as those species present once equilibrium is achieved. These data are expected to aid in the development of pharmacokinetic and toxicokinetic studies and to further the understanding of the fate of fluoride, including its interactions with other species in drinking water. As such, the results of this study will be of use to state agencies, water utilities, and other governmental or scientific bodies who seek to ensure the quality of the nation ‘s drinking water supplies.

2.2 Objective

The primary objective of this RFA is to investigate the reactions that take place when fluorosilicates are added to drinking water supplies and what concentrations of which fluorosilicate species may [sic]monitored in finished drinking water supplies and what techniques may be used for such monitoring…” (Emphasis added)

The bold italicized text is a remarkable admission by the US EPA that their experts (Urbansky and Schock) may have been mistaken in the position they published in 2000 as an official work piece of the EPA “proving” that Coplan and Masters couldn’t possibly be right. This attack on me and my colleague has been widely and repeatedly cited. You are among the many. It now appears EPA management is uncertain of the published claims of their experts. But, I don’t expect to live long enough to see a retraction.

Calling your attention to this new position of the EPA is not in the nature criticism of your work. It is simply a caveat; you might do a little more homework while you have the opportunity. It just might be possible Coplan and Masters have not been fools after all.

Indeed, that possibility has been given some credence by other US toxicology authorities.

The NTP and ICCEC have both considered the need for toxicological studies of drinking water treated with silicofluorides. Fluosilicic acid and sodium fluosilicate now appear on the list of nominations for study by the NTP. In connection with that process, the NTP commissioned an extensive literature survey that can be found at – http://ntp.niehs.nih.gov/ntp/htdocs/Chem_Background/ExSumPDF/Fluorosilicates.pdf

Having given you these “freebies,” let me turn to your treatise by starting with its first fundamental premise and main conclusion which reiterates previously emphasized text.

“Hexafluorosilicate added to water is effectively 100% dissociated to form fluoride ion under water treatment conditions. Therefore in terms of chemistry and bioavailability there is absolutely no difference between “added” and natural fluoride.”

The Fundamental Premise Is False

One is expected to believe that water already bearing fluoride provided by nature is ipso facto free of toxins and harmless. That may be true for some naturally “fluoridated” water, but it is certainly not true of others. Indeed, as far back as 1906 a German study (Sahlbom N and Hinrichsen FW; “Titration der Kieselfluorwasserstoffsaure”; Berichte ; 1906, No. pp 2609-2611) was measuring radioactivity and fluosilicate in thermal waters of Aachen. In the 1950s and 1960s Ionel Rapaport, an endocrinologist, was studying the prevalence of Down Syndrome as a function of naturally fluoridated water in the upper Midwest of the United States. More recently, studies in India found that fluorosis was much worse where silicon occurred together in natural water with a fluoride content in the range of low parts per million (Anasuya A, Bapurao S, Paranjape PK J; “Fluoride and silicon intake in normal and endemic fluorotic areas”; Trace Elem Med Biol 1996 Sep;10(3):149-55). The naturally occurring silicon was certainly not present in elemental form, it was most likely incorporated in a fluosilicate.

The most interesting piece of evidence on this subject, however, comes out of my own work with Professor Masters. During our studies of Massachusetts children’s blood lead.

I found a “cluster” of towns sharing the same geology whose children had blood lead values comparable to the city of Boston and two to three times higher than other towns comparable in demographic, economic, racial, and other terms. The “Ware Cluster” (as I dubbed it) were the only communities in Massachusetts that reported having “natural fluoride” and the fluoride values were in the typical low ppm range.

You are to be congratulated in stating that “…there is absolutely no difference between ‘added’ and natural fluoride.” The flaw in your argument is that it assumes that natural fluoride is innocuous. It is not. And, our evidence on that score is that adverse health and behavior effects are observed to similar extents whether the local water is treated with one of the silicofluorides or the fluoride is delivered by nature.

The important distinctions we have observed are between silicofluoride treated water and either non-fluoridated water or water treated with sodium fluoride. The question that might be asked by a real scientist would be: “What is different about both water bearing natural fluoride and silicofluoride treated water which distinguishes them from water treated with simple sodium fluoride or not fluoridated at all?” There are at least two possible answers.

One is that fluosilicate is simply a “marker” for some toxin or group of toxins that do not occur in non-fluoridated or NaF treated water. There are excellent reasons here. The concurrent presence of “natural” fluoride with radio-decay progeny of uranium is well-established from the Scandavian countries and Central Europe to Iowa. For various reasons not relevant here, these progeny are both alpha particle-emitters and gamma radiators. The damage done by alpha particle-emitters inhaled and/or digested from food or drink is without doubt a serious consideration. There is a reasonable likelihood that this is a risk from both “natural fluoride” and silicofluoride fluoridated water that does not accompany sodium fluoride or non-fluoridated water.

The second feature distinguishing sodium fluoride from silicofluoride has to do with the inherent differences in the mechanisms for release of free fluoride. Interestingly, your treatise on page 9 indicates that NaF at 100 ppm would be 99.998% dissociated. On the other hand, this is far from the case for the silicofluoride anion. Its dissociation path and extent are still debated despite the EPA experts, CDC dentists, at least a dozen other scientists who have published on the subject during the 20th Century, and now you.

Dissociation of Silicofluoride Is NOT Complete

Your first conclusion and the principal message of your text is that at 1 ppm of fluoride, silicofluoride is “effectively 100% dissociated.” That must mean that for every 100 silicofluoride anions very close to 600 fluoride anions have been released and available as free fluoride ion. If so, why is it necessary to do fluoride ion specific electrode measurements only after treating a test sample of fluoridated water with TISAB solution?

But, forget that for the moment and consider some simple chemical arithmetic for “99 %” dissociation. If all but 1% (ie 6 out of 600) of the bound fluoride ions are still bound to a silicon core atom, then 6% of the residues of the original silicofluoride anions are still complexes of fluoride with silicon. Does this qualify as “effectively 100% dissociated” hexafluorosilcate? But there is more here than meets the eye. Perhaps you are not aware of other considerations.

Free fluoride is a very effective catalyst for silicic acid polymerization (otherwise called “condensation” or oligomerization.”) As a stream of 24 % strength fluosilicic acid enters a body of water it cannot instantaneously be diluted by several orders of magnitude. Over the time frame of molecular reaction events, solution/dilution proceeds rather slowly. So before a final dilution to 1 ppm has been arrived at a fair amount of free fluoride has been hanging around in the vicinity of partially fluorinated silicic acid. Is it not conceivable that some fraction of liberated mono-silicic acid enters siloxane bonds with silicic acid moieties that still carry one of those six fluorines left on a silicon core?

In explicitly realistic terms, dimerized molecules with one fluoride still bound could comprise about 12% by weight of the “effectively 100% dissociated” hexafluorosilicate anions. Shall I go on? Let me assure you that there is plenty of evidence for fluosiloxane formation due to silicofluoride dissociation water. The fact is that neither Urbansky/Schock nor you can dispute the validity of this suggestion. On the other hand, perhaps that is what you meant to convey by the following statement in your text at page 9:

“The extent to which the hexafluorosilicate ion, SiF6 2-, dissociates to form fluoride ion (F-) and silicic acid [Si(OH)4] at equilibrium can be calculated from the hydrolysis constant Khyd for the reaction….”

Underlining the phrase “at equilibrium” is a pregnant proviso. What produces the equilibrium you require? On the one hand, you suggest that water plant conditions result in such an equilibrium, but then enumerate several situations making neat assumptions of theoretical chemistry less than convincing. As a matter of fact there is a lot of empirical evidence for that from experiments in which samples of fluosilicic acid are raised to pH 9 at the boil for ten minutes in order to detect all possible available fluoride ion. Is that what equilibrium means to you? (Incidentally, did I miss some mention of TISAB use in your treatise? Wouldn’t that have been an appropriate matter to discuss in the sections devoted to fluoride complexing with aluminum and iron?)

By the way, a so-called “expert” carrying the exalted title of “Senior Toxicologist and Chemical Manager for Fluorides” at the ATSDR lectured me on the difference between causation and correlation. Lest you assume similar limitations on my knowledge of chemistry, bear with me in a moment of reminiscence about my fee-for-service professional career that might interest you.

In the early 1950s I had to solve a very complex problem in probability statistics. Assuming that answers to my quandary should be easier, I visited an expert at MIT hoping for a quick resolution. He listened carefully, asked questions and concluded: “Mike, you’re working on the frontier of this field.” Without his help, my colleague and I went on and published our work, nevertheless.

In due course we engaged in a collegial exchange with a UK team doing similar work. The letters to the Editor of the Journal of the Textile Institute reached an acerbic quality. A British referee expert (M. Hannah) was called in to settle the dispute; she concluded that Coplan and Klein had developed the “more powerful” method of doing the probability statistics. I was teaching statistics myself before John Risher, the ATSDR expert who wanted to explain correlation to me had, even seen his first dawn.

In over 45 years of successful consulting in polymer science, chemical engineering processes, chemistry, and other fields including water and waste water treatments, I served many companies, including one of the largest phosphate fertilizer producers. In another field I first met Jack Welch when he ran a plastics plant in Selkirk NY and by the time he was Chairman of GE, I had done 28 consulting projects for that little company.

Throughout my direct hands-on activities and the supervision of dozens of scientists in many disciplines I earned a reputation for being tough on myself as well as “telling it the way it is” when dealing with clients, subordinates, and colleagues. I would welcome the opportunity to inaugurate you into that latter fraternity.

Thank you for drawing my attention to this publication. In view of the need to provide a balanced analysis of this contentious subject, all reputable analyses of the issues relating to the use of unlicensed medicinal substances for public medication are welcome, provided that they comply with appropriate standards of scientific methodology and validity.

Unfortunately, in this case, I consider that the paper has no value in clarifying any of the issues concerned. It is an excellent example of theoretical modelling carried out in apparent isolation from the inconvenient field data that testifies to the existence of effects that the authors appear to be either ignorant of, or else to have rejected for undisclosed reasons.

Their introductory background statement (s.1.1, p3) refers solely to the York Review. Yet there is no discussion – there or elsewhere – of the merits of any of the extensive peer criticism of that source, implying that it is therefore reliable and comprehensive source. It is not, because there were stringent exclusions on the range of evidence that the Panel was permitted to consider. So it is remarkable that in their Appendix to the WRc paper the authors should choose to offer two papers on the effects of fluoride and aluminium in drinking water in rats and rabbits – the York Review was specifically prohibited from drawing from animal experimentation sources.

As for the body of the paper, it is regrettable that the range of sources of published data on this subject drawn on by the authors appears to be seriously unbalanced. Most of the relevant core research publications on the topic on which of the analysis is based – the dissociation of silicofluorides in water under conditions actually occurring in industrial water treatment – should be absent from the discussion.

I am unqualified to comment on whether the conclusions presented in the subsequent sections, dealing with interactions between fluoride as such and other metals, might be affected by the defects evident in the first section. My comments are therefore directed towards what I see as a lack of consideration of established laboratory and field observations that contradict the analysis in the core argument as presented in Section 2. One does not need to be a specialist in this field – like many others I would wish simply to be provided with a clearly presented arguments of both the evidence for and against the authors’ analysis, and appropriate conclusions based on all of that evidence.

In this case, the authors have failed to provide that coverage. Their main conclusion relevant to the fluoridation debate is that theoretical calculations of the dissociation characteristics of silicofluorides in water indicate that there is “absolutely no difference” in terms of chemistry and bioavailability of the silicofluorides used in so-called ‘water treatment’ and those of the simple metal fluorides present in water subject to “natural fluoridation”. There is reputable peer-reviewed and published literature contradicting this conclusion. The only way that such a claim can be made is by constructing an abstract theoretical model, then failing to validate the conclusions against relevant experimental investigations, either on the part of the authors themselves or using experimental data taken from published field studies elsewhere. Until any model is validated (and in the present case, under relevant field conditions), it can not be relied upon for guidance in the real world.

This technique of analysis by intellect is by no means new. As far back as 1957 Feldman, Morken and Hodge attempted to establish that silicofluorides dissociate completely in water. Recently Coplan has severely criticised documents used in the ‘Review of Toxicological Literature’ on silicofluoride toxicity (Integrated Laboratory Systems, October 2001) in the USA, in which he says of the Feldman et al. paper, “the authors of the article mean to “guarantee” the health safety of SiFs not by animal tests, but by theoretical chemical predictions of SiF dissociation.

In 1975 – a quarter of a century ago – laboratory studies by Westendorf in Germany showed that silicofluorides do not dissociate completely, and that water containing these chemicals has a distinct neurotoxic effect acetylcholinesterase inhibition) that does not occur under identical conditions in the presence of simple metal fluorides. This paper is now extensively quoted in the literature, and has been greatly expanded upon recently by a number of researchers, notably by Masters and Coplan. in the USA Yet no references to these recent studies are included in the WRc paper.

The authors go to some length to show that the levels of metallic contaminants from the industrial sources of silicofluorides in potable fluoridated water are well below the limits set for them by the Drinking Water Inspectorate and other regulatory bodies. But what they do not disclose or discuss is that silicofluorides – at the levels used in water fluoridation – are in some way associated with a clear increase in uptake of lead from an entirely separate source – the external environment – and that this is particularly significant in juveniles. Masters and Coplan have carried out three separate studies, involving 400,000 children in New York, Greater Boston, and nationally in 80 counties across the States. They report that “SiF-treated municipal water is ALWAYS significantly associated with increased blood lead levels in children”.

They specifically exclude the source of this lead originating from any impurities in the silicofluoride chemicals themselves. In each case, those exposed to silicofluoride-treated water are more likely to have behavioural or health problems. They note that such problems – including hyperactivity, substance abuse and violent crime – are clinically associated with lead poisoning.

Children’s blood lead levels in areas that are fluoridated with sodium fluoride are not significantly different to those in unfluoridated areas, once other environmental effects such as poverty are allowed for. Clearly, these studies provide evidence of some residual toxicity issue in the use of silicofluorides that the authors of the WRc-NSF paper have failed to address.

The absence of any discussion of these important publications in the WRc-NSF paper renders its primary conclusion on silicofluoride dissociation unreliable. The literature pertaining to this subject, and of the toxic effects of the use of these substances under actual industrial application and public exposure in the water sector are all easily available, both from the original publication sources and the Internet. The failure of the authors to refer to or discuss these sources is a major defect of the paper. They should perhaps consider whether it might be prudent to retract and revise their work to take account of additional information on this subject.

Yours sincerely

Doug Cross

Environmental Analyst and Forensic Ecologist

To Dr Peter Jackson from Jane Jones, Campaign Director, NPWA:

Dear Dr Jackson

Our attention was drawn to your paper, “Chemistry and bioavailability aspects of fluoride in drinking water”. Report No, CO 5037, WRc-NSF Ltd., which appears on the British Fluoridation Society website – http://www.bfsweb.org/documents/wrcreport.pdf We have a number of comments to make, particularly on the issue of dissociation.

In your report, “Chemistry and bioavailability aspects of fluoride in drinking water – an authoritative independent review of the chemical speciation and bioavailability of fluoride in drinking water,” posted on the British Fluoridation website, you stated: “Hexafluorosilicate added to fluoridate water is effectively 100% dissociated to form fluoride ion under water treatment conditions. Therefore in terms of chemistry and bioavailability there is absolutely no difference between added and ‘natural’ fluoride.”

There seem to be “script writing errors” in the document which make it impossible to thoroughly review your paper. However, despite the missing pages, we can see that the review was based on computer modeling rather than on physical chemistry which means that you are working with hypotheticals, as were Urbansky and Schock, whom you cite (Urbansky, E.T., and Schock, M.R.. Can fluoridation affect water lead levels and lead neurotoxicity? In: American Water Works Association Annual Conference Proceedings, Denver, CO, June 11-15, 2000).

Even Urbansky and Schock, in their more comprehensive paper, were not so optimistic as to claim that H2SiF6 dissociates 100% in drinking water!

Your paper ignored the 1969 Crosby study, (cited by Urbansky & Schock), which WAS based on physical chemistry. In that paper, Crosby stated that 100% dissociation was unlikely to occur. The best he found was between 97% – 99% dissociation of the fluorosilicate radical. He also inserted a caveat – ‘under the conditions chosen for the experiment’. (Crosby, N.T.; Equilibria of Fluorosilicate Solutions with Special Reference to the Fluoridation of Public Water Supplies. J. Appl. Chem., 1969, 19(4), 100.).

Both Urbansky & Schock and Crosby suggest that the existence of the SiF radical is dependent on the pH of the water. However, the researchers did not acknowledge that fluoride in alkaline AND acidic solutions, etches glass.

It reads: “The release of fluoride proceeds through a complex, multi-step equilibrium process that is not well-understood . . . The primary objective . . . is to investigate the reactions that take place when fluorosilicates are added to drinking water supplies and what concentrations of which fluorosilicate species may be monitored in finished drinking water supplies.”

Chemical engineers were aware of fluoride/silica interaction in aqueous solution in the 1940s and recommended the use of sodium fluoride to inhibit silica scaling in boilers. “Fluoridation will provide all or part of the fluorides needed to remove silica from boiler water. An ion exchange process is reported to require 1.0 ppm fluoride for each 0.5 ppm silica removed. On the other hand, if sodium silicofluoride is used for fluoridation, about 0.5 ppm silica is formed when 1.0 ppm is added from this source. (Bauman, et al, Silica Free Boiler Water by Ion Exchange, Ind. Eng. Chem. 39:1453, 1947 cited in Maier, F.J; Fluoridation of Public Water Supplies. J. Am. Waterworks Assn. 42:1120-1132, 1950.)

In a 2001 reply to enquiry, Westendorf wrote: “. . . During hydrolysis we got a continuous shifting of the mobility, indicating that the different forms of hydrolysis with 2-6 fluorine at the Si are present at the same time, ending up at the more stable form of Si(OH)4F2. If we increased the pH to 9 and higher, a total hydrolysis occurs.”

The Water Research Centre is apparently not prepared to do a thorough review of the literature, nor to undertake physical testing of its own volition. In the recent past you threatened to charge us for answering our legitimate questions. We would therefore be interested to know who commissioned you to produce a piece of theoretical modelling, which cannot be taken seriously when work based on physical chemistry already exists. One wonders what were they are hoping to achieve!